U.S. patent number 6,358,914 [Application Number 09/335,128] was granted by the patent office on 2002-03-19 for surfactant compositions with enhanced soil release properties containing a cationic gemini surfactant.
Invention is credited to Manilal S. Dahanayake, Paul-Joel Derian, Gladys S. Gabriel, Robert Gabriel.
United States Patent |
6,358,914 |
Gabriel , et al. |
March 19, 2002 |
Surfactant compositions with enhanced soil release properties
containing a cationic gemini surfactant
Abstract
Compositions are disclosed comprising a conventional surfactant,
a cationic or amphoteric gemini surfactant and a polymeric soil
release agent. The conventional surfactant comprises a hydrophilic
group and a hydrophobic group. The gemini surfactant comprises two
surfactant moieties attached to each other by a spacer moiety. Each
surfactant moiety having at least one hydrophilic group and at
least one hydrophobic group. Novel trimeric and tetrameric cationic
gemini surfactants are also disclosed along with their use in
combination with soil release polymer compositions that exhibit
superior cleaning efficacies when incorporated in laundry and other
cleaning detergent systems. Novel surfactant/soil release polymer
compositions are also disclosed employing known cationic gemini
surfactants. The polymeric soil release agent can be any
conventional polymeric soil release agent, but preferably
comprising PET--POET copolymer. The compositions are useful as
surfactant additive packages, detergents and fabric softeners.
Inventors: |
Gabriel; Gladys S. (Cranbury,
NJ), Gabriel; Robert (Cranbury, NJ), Dahanayake; Manilal
S. (Princeton Junction, NJ), Derian; Paul-Joel (St.
Jean/St. Maurice-sur-Loire, FR) |
Family
ID: |
23310381 |
Appl.
No.: |
09/335,128 |
Filed: |
June 17, 1999 |
Current U.S.
Class: |
510/528; 510/276;
510/299; 510/329; 510/330; 510/400; 510/504; 510/515; 510/517 |
Current CPC
Class: |
C11D
1/65 (20130101); C11D 1/835 (20130101); C11D
1/94 (20130101); C11D 3/0036 (20130101); C11D
3/3715 (20130101); C11D 1/62 (20130101) |
Current International
Class: |
C11D
1/38 (20060101); C11D 1/65 (20060101); C11D
1/835 (20060101); C11D 1/94 (20060101); C11D
1/88 (20060101); C11D 3/37 (20060101); C11D
3/00 (20060101); C11D 1/62 (20060101); C11D
001/62 (); C11D 003/37 () |
Field of
Search: |
;510/276,329,330,299,400,504,515,517,528 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
R Zana et al., "Micellization of Two Triquaternary Ammonium
Surfactants in Aqueous Solution"; Langmuir. Jul. 5, 1995. .
R. Zana et al., "Alkanediyl-A,W-bis(dimethylalkylammonium bromide)
Surfactants. 1. Effect of the Spacer Chain Length on the Critical
Micelle Concentration and Micelle Ionization Degree"; Langmuir
(1991); 7, 1072-1075. .
M. Rosen et al., "Gemini Surfactants", Journal of Surfactants and
Detergents, vol. 1, No. 4 (Oct. 1998), pp. 547-554. .
M. Rosen, "Geminis: A New Generation of Surfactants"; Chemtech,
Mar. 1993, pp. 30-33. .
F. M. Menger et al., "Gemini Surfactants: A New Class of
Self-Assembling Molecules"; J. American Chemical Soc., 115, pp.
10083-10090 (1993)..
|
Primary Examiner: Boyer; Charles
Attorney, Agent or Firm: Watov & Kipnes, P.C.
Claims
What is claimed is:
1. An enhanced soil release detergent composition comprising:
a) a conventional surfactant having one hydrophobic group and one
hydrophilic group per molecule;
b) a cationic gemini surfactant of the formula: ##STR38##
wherein R1 independently represents alkyl, hydroxy-substituted
alkyl or perfluorinated alkyl of from about 5 to about 22 carbon
atoms; R2 represents alkylene, hydroxy-substituted alkylene or
alkylaryl of 1 to about 10 carbon atoms and the hydroxy-substituted
derivatives thereof or R3--D--R3 wherein R3 independently
represents alkylene of from 1 to about 6 carbon atoms and the
hydroxy-substituted derivatives thereof as well as aryl, and D
represents --O--, --S--, --SO2--, a polyether group [--O(R4)x--] or
aryl wherein R4 independently represents alkyl of from about 2 to
about 4 carbon atoms with x being a number from 1 to 20 and: X
independently represents an alkyl of 1 to 10 carbon atoms and the
hydroxy-substituted derivatives thereof and alkylaryl: and Y
independently represents an anion;
c) a polymeric soil release agent.
2. The composition of claim 1, wherein the conventional surfactant
is selected from the group consisting of nonionic, anionic,
cationic, amphoteric surfactants and mixtures thereof.
3. The composition of claim 2, wherein the conventional surfactant
comprises an anionic surfactant.
4. The composition of claim 3, wherein the anionic conventional
surfactant is selected from the group consisting of a fatty acid
soap, an ether carboxylic acid and salt thereof, an alkane
sulfonate salt, an alpha-olefin sulfonate salt, a sulfonate salt of
a higher fatty acid ester, a higher alcohol sulfate ester salt,
fatty alcohol ether sulfate salts, an alkaryl sulfate, sulfonate or
salt thereof, a higher alcohol phosphate ester salt, and a fatty
alcohol ether phosphate ester salt, an alkyl glycerol sulfonate,
sulfate or salt thereof, and a condensate of higher fatty
acids.
5. The composition of claim 2, wherein the conventional surfactant
is a cationic surfactant.
6. The composition of claim 5 wherein the conventional cationic
surfactant is the reaction product of higher fatty acids with a
polyamine selected from the group consisting of
hydroxyalkylalkylenediamine, dialkylenetriamine, and mixtures
thereof.
7. The composition of claim 5 wherein the conventional cationic
surfactant is selected from the group consisting of an
alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an
alkyldimethylbenzylammonium salt, an alkylpyridinium salt, an
alkylisoquinolinium salt, benzethonium chloride, and an acylamino
acid type cationic surfactant.
8. The composition of claim 2 wherein the conventional surfactant
is an amphoteric surfactant.
9. The composition of claim 8, wherein the amphoteric conventional
surfactant is selected from the group consisting of an amino acid,
betaine, sultaine, phosphobetaine, an imidazoline amphoteric
surfactant, soybean phospholipid, and yolk lecithin.
10. The composition of claim 8 wherein the amphoteric conventional
surfactant is selected from the group consisting of alkali salts of
alkyl amphocarboxyglycinates, alkyl amphocarboxypropionates, alkyl
amphodipropionates, alkyl amphodiacetates, alkyl amphoglycinates,
alkyl amphopropyl sulfonates and alkyl amphopropionates wherein
alkyl represents an alkyl group having 6 to 20 carbon atoms.
11. The composition of claim 2, wherein the conventional surfactant
comprises a nonionic surfactant.
12. The composition of claim 11 wherein the nonionic conventional
surfactant is selected from the group consisting of:
polyethylene oxide condensates of alkyl phenols;
condensation products of aliphatic alcohols with from about 1 to
about 25 moles of ethylene oxide;
condensation products of ethylene oxide with a hydrophobic base
formed by the condensation of propylene oxide with propylene
glycol;
condensation products of ethylene oxide with the reaction products
of propylene oxide with ethylenediamine;
water soluble amine oxides, phosphine oxides or sulfoxides each
having one alkyl moiety of from about 10 to 18 carbon atoms and two
moieties selected from the group consisting of alkyl groups and
hydroxy alkyl groups containing from about 1 to 3 carbon atoms;
and
mixtures thereof.
13. The composition of claim 11, wherein the nonionic conventional
surfactant is selected from the group consisting of a fatty acid
glycerine ester, a sorbitan fatty acid ester, a sucrose fatty acid
ester, a polyglycerine fatty acid ester, a higher alcohol ethylene
oxide adduct, a single long chain polyoxyethylene alkyl ether, a
polyoxyethylene alkyl allyl ether, a polyoxyethylene lanolin
alcohol, a polyoxyethylene fatty acid ester, a polyoxyethylene
glycerine fatty acid, a polyoxyethylene propylene glycol fatty acid
ester, a polyoxyethylene sorbitol fatty acid ester, a
polyoxyethylene castor oil or hardened castor oil derivative, a
polyoxyethylene lanolin derivative, a polyoxyethylene fatty acid
amide, a polyoxyethylene alkyl amine, an alkyl pyrrolidone,
glucamides, alkylpolyglucosides, a mono or dialkanol amide, a
polyoxyethylene alcohol mono or diamide, and an alkylamine oxide.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to compositions and methods of use of
both novel and known cationic or amphoteric surfactants which allow
for the better deposition of polymeric soil release agents with
surfactant systems. More particularly, the present invention
relates to compositions and methods of use of low concentrations of
surfactants comprised of multiple hydrophilic and hydrophobic
chains which allow for the improved deposition of polymeric soil
release agents in the presence of typical detergent ingredients,
especially highly anionic surfactant systems.
2. Background Discussion
Soil release agents are key ingredients in cleaning, e.g., textile
laundry and hard surface such as carpet-cleaning; and textile
treating.
These soil release agents are commonly applied during manufacture
of clothing or textile fiber. The primary purpose of the soil
release agents is to make it easier to clean the textile fibers by
home cleaning methods using conventional household machines or
cleaners.
For example, in laundering processes normally employed, such as
washing in a conventional home washing machine or hand washing with
detergent bars, it is usually very difficult to remove soil and/or
oily stains from textile material. Moreover, assuming that the
undesirable materials are removed from the textile and/or a fairly
clean textile material is being washed, soil remaining in the wash
water is often redeposited onto the textile material prior to the
end of the wash cycle. Hence, when the textile material is removed
from the washing machine and subsequently dried, it has not been
properly cleaned. Thus, textile material after use rarely assumes a
truly clean appearance, but instead tends to gray and/or yellow due
to the soil and/or oily materials deposited or redeposited and
remaining thereon.
Also, synthetic fibers, and, therefore, fabrics having synthetic
fibers incorporated therein or made entirely of synthetic fibers,
are hydrophobic and oleophilic. Therefore, the oleophilic
characteristics of the fiber permit oil and grime to be readily
embedded in the fiber, and the hydrophobic properties of the fiber
prevent water from entering the fiber to remove the contaminants
from the fiber.
One remedy to the soil removal and soil redeposition problem is to
deposit a finish onto the fiber to impart a hydrophilic character
to the fiber. Attempts have been made to reduce the oleophilic
characteristics of these synthetic fibers by coating the fibers
with a coating that is oleophobic, i.e., will hinder the attachment
of soil and oil materials to the fibers. Many polymer systems have
been proposed which are capable of forming a film around the fibers
that constitute the textile material, particularly acid emulsion
polymers prepared from organic acids having reactive points of
unsaturation. These treating polymers are known as soil-release
agents.
Typical of the soil release agents that have been developed for
synthetic fibers and fabrics, are the copolymers of ethylene glycol
and terephthalic acid for the treatment of Dacron, Fortrel, Kodel
and Blue C Polyester, trademarks of various synthetic fibers and
fabrics.
Among the leading soil release agents developed for laundering
purposes are the polyesters exemplified in U.S. Pat. Nos.
3,962,152; 3,416,952; 4,132,680; 4,201,824; 4,423,557; 4,349,688;
3,959,230; 3,893,929; 3,712,873; and 4,116,885. Generally these
agents are polyester polymers containing terephthalate and/or
urethane groups to improve water compatibility.
The term "soil-release" in accordance with the present invention
refers to the ability of the fabric to be washed or otherwise
treated to remove soil and/or oily materials that have come into
contact with the fabric. The present invention does not wholly
prevent the attachment of soil or oil materials to the fabric, but
hinders such attachment and improves the cleanability of the
fabric.
Concentrated solutions of soil-release polymers have been padded
onto fabrics by textile manufacturers to impart a permanent
soil-release finish to the fabric. As the amount of soil-release
polymer on the fabric is increased, the ability of the fabric to
release soil is increased. However, fabrics with this permanent
soil-release finish possess many disadvantages. As the amount of
soil-release polymer on the fabric is increased, the fabric has a
tendency to become stiff and lose the desirable hand characteristic
of the fabric. Thus, the upper limit on the amount of soil-release
polymer to be used is determined by economics and the resulting
adverse effect on the fabric. Fabrics with a heavy application of
soil-release polymer do not have the same desirable appearance and
hand as the same fabrics without the soil-release coating. Thus,
practically speaking, there is a set concentration range of
soil-release agent that can be applied, dictated by commercial
requirements.
Some soil-release polymers are effective fabric treating agents
even at very low levels on the fabric, at which levels the
appearance and hand of the fabric are not adversely affected. Thus,
this property offers an ideal method of treating a synthetic fiber
containing fabric which would be to reapply a very small amount of
soil-release polymer to the fabric each time the fabric is
washed.
Moreover, the soil release agent is preferably reapplied when the
fabric is washed because the original soil release agent, applied
to the fabric during manufacture, washes out after repeated washing
by the consumer.
The problem is to get the soil release agent in the detergent
solution to adequately deposit and remain on the clothing being
washed. A number of theories have been proposed to explain the
difficulties encountered when one tries to enhance this soil
release agent deposition during wash process. One theory suggests
that the surfactants in the detergent may complex with the soil
release agent, thus inhibiting the deposition of the agent onto the
fabric. Another theory has proposed that the surfactants in the
detergent compositions compete with the soil release agents for
sites on the fabric. This competition prevents the soil release
agents from getting to the fabric.
Anionic surfactants such as alkylbenzenesulfonates, alkylether
sulfates, etc., are known to have antagonistic effects on the
polymer deposition. These antagonistic effects are further
exacerbated because anionic surfactants are generally used at high
concentrations for general soil and stain removal performance.
While conventional surfactants generally have one hydrophilic group
and one hydrophobic group, recently a group of compounds having at
least two hydrophobic groups and at least two hydrophilic groups
per molecule have been introduced. These have become known as
"gemini surfactants" in the literature, e.g., Chemtech, March 1993,
pp 30-33, and J. American Chemical Soc., 115, 10083-10090 (1993)
and the references cited therein. Other gemini surfactant
compounds, that is, compounds having at least two hydrophilic
groups and at least two hydrophobic groups are also disclosed in
literature, but often are not referred to expressly as gemini
surfactants.
Prior to the present invention, many synergistic benefits of
mixtures of gemini surfactants and other ingredients were unknown.
It would be a major achievement to provide a detergent composition
that would enhance deposition of soil release agents on textile
material being washed by the consumer and, thus, provide lasting
soil release properties for the life of the material.
OBJECTS OF THE INVENTION
An object of the present invention is to provide detergent
compositions with enhanced soil release properties.
Another object of the present invention is to provide textile
detergent compositions comprising conventional surfactants and soil
release agents with both novel and known surfactants comprised of
multiple hydrophilic/hydrophobic chains.
Another object of the present invention is to provide detergency
and soil release benefits in compositions which also act as fabric
softeners.
These and other objects will become apparent from the description
of the invention in the present specification.
SUMMARY OF THE INVENTION
The present invention relates to detergent compositions having
enhanced soil release properties. These compositions comprise a
first surfactant, a second cationic or amphoteric surfactant and a
soil release agent. The first surfactant referred to is a
conventional surfactant and has a single hydrophobic group and a
single hydrophilic group per molecule. The second surfactant is a
cationic or amphoteric surfactant having at least two hydrophobic
groups and at least two hydrophilic groups per molecule. Those
comprised of two hydrophilic/hydrophobic chains are known as gemini
surfactants. Preferably, the hydrophilic groups are the same and
the hydrophobic groups are the same. The second surfactant may also
consist of a novel class of cationic surfactants comprised of more
than two hydrophilic/hydrophobic chains as well as the use of
cationic and amphoteric gemini surfactants known in the art. The
soil release agents useful in the compositions of the present
invention can be any of the conventional soil release agents known
by those skilled in the art. However, nonionic polymer soil release
agents are preferred.
It has been unexpectedly found that blends of these multiple
hydrophilic/hydrophobic chain surfactants with certain conventional
anionic, nonionic, cationic and amphoteric surfactants provide
synergistic effects with respect to the deposition and maintenance
of soil release agents on the washed substrate, e.g., textiles.
Serendipitously, the present invention not only promotes the
deposition of soil release agents, but also enhances soil removal,
general detergency, and secondary properties such as soil
anti-redeposition.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The detergent compositions of the present invention achieve their
unexpectedly superior soil release properties by combining a first
surfactant, a second cationic or amphoteric surfactant comprised of
multiple hydrophilic/hydrophobic chains and a soil release agent.
The first surfactant is selected from conventional well known
non-gemini surfactants discussed in detail below. The second
surfactant is selected from certain cationic or amphoteric
surfactants comprised of multiple hydrophilic/hydrophobic chains
and the soil release agent is selected from conventional well known
soil release agents also discussed in detail below.
I. First Conventional Surfactants
In contrast to second (gemini) surfactants, the first or
conventional surfactants have only a single hydrophobic group
(head) and a single hydrophilic group (tail). It should be apparent
that even non-gemini amphoteric surfactants, having a hydrophilic
group with both positive and negative charges, is defined as having
only a single hydrophilic group.
A. Nonionic Surfactants
Nonionic surfactants, including those having an HLB of from 5 to
17, are well known in the detergency art. Examples of such
surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued
Feb. 20, 1973, and U.S. Pat. No. 3,332,880, Kessler et al., issued
Jul. 25, 1967, each of which is incorporated herein by reference.
Nonlimiting examples of suitable nonionic surfactants which may be
used in the present invention are as follows:
(1) The polyethylene oxide condensates of alkyl phenols. These
compounds include the condensation products of alkyl phenols having
an alkyl group containing from about 6 to 12 carbon atoms in either
a straight chain or branched chain configuration with ethylene
oxide, said ethylene oxide being present in an amount equal to 5 to
25 moles of ethylene oxide per mole of alkyl phenol. The alkyl
substituent in such compounds can be derived, for example, from
polymerized propylene, diisobutylene, and the like. Examples of
compounds of this type include nonyl phenol condensed with about
9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol
condensed with about 12 moles of ethylene oxide per mole of phenol;
dinonyl phenol condensed with about 15 moles of ethylene oxide per
mole of phenol; and diisooctyl phenol condensed with about 15 moles
of ethylene oxide per mole of phenol. Commercially available
nonionic surfactants of this type include Igepal CO-630, marketed
by Rhone-Poulenc Inc. and Triton X-45, X-114, X-100, and X-102, all
marketed by Union Carbide.
(2) The condensation products of aliphatic alcohols with from about
1 to about 25 moles of ethylene oxide. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary or
secondary, and generally contains from about 8 to about 22 carbon
atoms. Examples of such ethoxylated alcohols include the
condensation product of myristyl alcohol condensed with about 10
moles of ethylene oxide per mole of alcohol; and the condensation
product of about 9 moles of ethylene oxide with coconut alcohol (a
mixture of fatty alcohols with alkyl chains varying in length from
10 to 14 carbon atoms). Examples of commercially available nonionic
surfactants in this type include Tergitol 15-S-9, marketed by Union
Carbide Corporation, Neodol 45-9, Neodol 23-6.5, Neodol 45-7, and
Neodol 45-4, marketed by Shell Chemical Company.
(3) The condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene
glycol. The hydrophobic portion of these compounds typically has a
molecular weight of from about 1500 to 1800 and exhibits water
insolubility. The addition of polyoxyethylene moieties to this
hydrophobic portion tends to increase the water solubility of the
molecule as a whole, and the liquid character of the product is
retained up to the point where the polyoxyethylene content is about
50% of the total weight of the condensation product, which
corresponds to condensation with up to about 40 moles of ethylene
oxide. Examples of compounds of this type include certain of the
commercially available Pluronic surfactants, marketed by Wyandotte
Chemical Corporation.
(4) The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylenediamine.
The hydrophobic moiety of these products consists of the reaction
product of ethylenediamine and excess propylene oxide, said moiety
having a molecular weight of from about 2500 to about 3000. This
hydrophobic moiety is condensed with ethylene oxide to the extent
that the condensation product contains from about 40% to about 80%
by weight of polyoxyethylene and has a molecular weight of from
about 5,000 to about 11,000. Examples of this type of nonionic
surfactant include certain of the commercially available Tetronic
compounds, marketed by Wyandotte Chemical Corporation.
(5) Semi-polar nonionic detergent surfactants include water-soluble
amine oxides containing one alkyl moiety of from about 10 to 18
carbon atoms and 2 moieties selected from the group consisting of
alkyl groups and hydroxyalkyl groups containing from 1 to about 3
carbon atoms; water-soluble phosphine oxides containing one alkyl
moiety of about 10 to 18 carbon atoms and 2 moieties selected from
the group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to 3 carbons atoms; and water-soluble
sulfoxides containing one alkyl moiety of from about 10 to 18
carbon atoms and a moiety selected from the group consisting of
alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon
atoms.
Preferred semi-polar nonionic detergent surfactants are the amine
oxide detergent surfactants having the formula ##STR1##
wherein R.sup.1 is an alkyl, hydroxy alkyl, or alkyl phenyl group
or mixtures thereof containing from about 8 to about 22 carbon
atoms. R.sup.2 is an alkylene or hydroxy alkylene group containing
from 2 to 3 carbon atoms or mixtures thereof, x is from 0 to about
3 and each R.sup.3 is an alkyl or hydroxy alkyl group containing
from 1 to about 3 carbon atoms or a polyethylene oxide group
containing from one to about 3 ethylene oxide groups and said
R.sup.3 groups can be attached to each other, e.g., through an
oxygen or nitrogen atom to form a ring structure.
Preferred amine oxide detergent surfactants are C.sub.10 -C.sub.18
alkyl dimethyl amine oxide, C.sub.8 -C.sub.18 alkyl dihydroxy ethyl
amine oxide, and C.sub.8-12 alkoxy ethyl dihydroxy ethyl amine
oxide.
Nonionic detergent surfactants (1)-(4) are conventional ethoxylated
nonionic detergent surfactants and mixtures thereof can be
used.
Preferred alcohol ethoxylate nonionic surfactants for use in the
compositions of the liquid, powder, and gel applications are
biodegradable and have the formula:
wherein R is a primary or secondary alkyl chain of from about 8 to
about 22, preferably from about 10 to about 20 carbon atoms and n
is an average of from about 2 to about 12, particularly from about
2 to about 9. The nonionics have an HLB (hydrophilic-lipophilic
balance) of from about 5 to about 17, preferably from about 6 to
about 15. HLB is defined in detail in Nonionic Surfactants, by M.
J. Schick, Marcel Dekker, Inc., 1966, pages 606-613, incorporated
herein by reference. In preferred nonionic surfactants, n is from 3
to 7. Primary linear alcohol ethoxylates (e.g., alcohol ethoxylates
produced from organic alcohols which contain about 20% 2-methyl
branched isomers, commercially available from Shell Chemical
Company under the trademark Neodol) are preferred from a
performance standpoint.
Particularly preferred nonionic surfactants for use in liquid,
powder, and gel applications include the condensation product of
C.sub.10 alcohol with 3 moles of ethylene oxide; the condensation
product of tallow alcohol with 9 moles of ethylene oxide; the
condensation product of coconut alcohol with 5 moles of ethylene
oxide; the condensation product of coconut alcohol with 6 moles of
ethylene oxide; the condensation product of C.sub.12 alcohol with 5
moles of ethylene oxide; the condensation product of C.sub.12-13
alcohol with 6.5 moles of ethylene oxide, and the same condensation
product which is stripped so as to remove substantially all lower
ethoxylate and nonethoxylated fractions; the condensation product
of C.sub.12-13 alcohol with 2.3 moles of ethylene oxide, and the
same condensation product which is stripped so as to remove
substantially all lower ethoxylated and nonethoxylated fractions;
the condensation product of C.sub.12-13 alcohol with 9 moles of
ethylene oxide; the condensation product of C.sub.14-15 alcohol
with 2.25 moles of ethylene oxide; the condensation product of
C.sub.14-15 alcohol with 4 moles of ethylene oxide; the
condensation product of C.sub.14-15 alcohol with 7 moles of
ethylene oxide; and the condensation product of C.sub.14-15 alcohol
with 9 moles of ethylene oxide. For bar soap applications, nonionic
surfactants are preferably solids at room temperature with a
melting point above about 25.degree. C., preferably above about
30.degree. C. Bar compositions of the present invention made with
lower melting nonionic surfactants are generally too soft, not
meeting the bar firmness requirements of the present invention.
Also, as the level of nonionic surfactant increases, i.e., above
about 20% by weight of the surfactant, the bar can generally become
oily.
Examples of nonionic surfactants usable herein, but not limited to
bar applications, include fatty acid glycerine and polyglycerine
esters, sorbitan sucrose fatty acid esters, polyoxyethylene alkyl
and alkyl allyl ethers, polyoxyethylene lanolin alcohol, glycerine
and polyoxyethylene glycerine fatty acid esters, polyoxyethylene
propylene glycol and sorbitol fatty acid esters, polyoxyethylene
lanolin, castor oil or hardened castor oil derivatives,
polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines,
alkylpyrrolidone, glucamides, alkylpolyglucosides, and mono- and
dialkanol amides.
Typical fatty acid glycerine and polyglycerine esters, as well as
typical sorbitan sucrose fatty acid esters, fatty acid amides, and
polyethylene oxide/polypropylene oxide block copolymers are
disclosed by U.S. Pat. No. 5,510,042, Hartman et al, incorporated
herein by reference.
The castor oil derivatives are typically ethoxylated castor oil. It
is noted that other ethoxylated natural fats, oils or waxes are
also suitable.
Polyoxyethylene fatty acid amides are made by ethoxylation of fatty
acid amides with one or two moles of ethylene oxide or by
condensing mono-or diethanol amines with fatty acid.
Polyoxyethylene alkyl amines include those of formula:
RNH--(CH.sub.2 CH.sub.2 O).sub.n --H, wherein R is C.sub.6 to
C.sub.22 alkyl and n is from 1 to about 100.
Monoalkanol amides include those of formula: RCONHR.sup.1 OH,
wherein R is C.sub.6 -C.sub.22 alkyl and R.sup.1 is C.sub.1 to
C.sub.6 alkylene. Dialkanol amides are typically mixtures of:
and
wherein R in the above formulas is an alkyl of from 6 to 22 carbon
atoms.
Examples of preferred but not limiting surfactants for detergent
bar products are the following:
Straight-chain Primary Alcohol Alkoxylates
The deca-, undeca-, dodeca-, tetradeca-, and pentadeca-ethoxylates
of n-hexadecanol, and n-hexadecanol, and n-octadecanol having an
HLB within the range recited herein are useful nonionics in the
context of this invention. Exemplary ethoxylated primary alcohols
useful herein as the conventional nonionic surfactants of the
compositions are n-C.sub.18 EO(10); n-C.sub.14 EO(13); and
n-C.sub.10 EO(11). The ethoxylates of mixed natural or synthetic
alcohols in the "tallow" chain length range are also useful herein.
Specific examples of such materials include tallow-alcohol-EO(11),
tallow-alcohol-EO(18), and tallow-alcohol-EO(25).
Straight-Chain Secondary Alcohol Alkoxylates
The deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, and
nonadeca-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol,
and 5-eicosanol having an HLB within the range recited herein are
useful conventional nonionics in the context of this invention.
Exemplary ethoxylated secondary alcohols useful herein are
2-C.sub.16 (EO).sub.11 ; 2-C.sub.20 (EO).sub.11 ; and 2-C.sub.16
(EO).sub.14
Alkyl Phenol Alkoxylates
As in the case of the alcohol alkoxylates, the hexa- through
octadeca-ethoxylates of alkylated phenols, particularly monohydric
alkylphenols, having an HLB within the range recited herein are
useful as conventional nonionic surfactants in the instant
compositions. The hexa- through octadeca-ethoxylates of
p-tridecylphenol, m-pentadecylphenol, and the like, are useful
herein. Exemplary ethoxylated alkylphenols useful in the mixtures
herein are: p-tridecylphenol EO(11) and p-pentadecylphenol EO(18).
Especially preferred is Nonyl Nonoxynol-49 known as Igepal.RTM.
DM-880 from Rhone-Poulenc Inc.
As used herein and as generally recognized in the art, a phenylene
group in the nonionic formula is the equivalent of an alkylene
group containing from 2 to 4 carbon atoms. For present purposes,
nonionics containing a phenylene group are considered to contain an
equivalent number of carbon atoms calculated as the sum of the
carbon atoms in the alkyl group plus about 3.3 carbon atoms for
each phenylene group.
Olefinic Alkoxylates
The alkenyl alcohols, both primary and secondary, and alkenyl
phenols corresponding to those disclosed immediately hereinabove
can be ethoxylated to an HLB within the range recited herein and
used as the conventional nonionic surfactants of the instant
compositions.
Branched Chain Alkoxylates
Branched chain primary and secondary alcohols which are available
can be ethoxylated and employed as conventional nonionic
surfactants in compositions herein.
The above ethoxylated nonionic surfactants are useful in the
present compositions alone or in combination, and the term
"nonionic surfactant" encompasses mixed nonionic surface active
agents.
Alkylpolysaccharides
Still further suitable nonionic surfactants of this invention
include alkylpolysaccharides, preferably alkylpolyglycosides of the
formula:
wherein
Z is derived from glycose;
R is a hydrophobic group selected from the group consisting of a
C.sub.10 -C.sub.18, preferably a C.sub.12 -C.sub.14, alkyl group,
alkyl phenyl group, hydroxyalkyl group, hydroxyalkylphenyl group,
and mixtures thereof;
n is 2 or 3; preferably 2;
t is from 0 to 10; preferably 0; and
x is from 1.5 to 8; preferably 1.5 to 4; more preferably from 1.6
to 2.7.
These surfactants are disclosed in U.S. Pat. No. 4,565,647 to
Llenado, issued Jan. 21, 1986; U.S. Pat. No. 4,536,318 to Cook et
al., issued Aug. 20, 1985; U.S. Pat. No. 4,536,317, Llenado et al.,
issued Aug. 20, 1985; U.S. Pat. No. 4,599,188 to Llenado, issued
Jul. 8, 1986; and U.S. Pat. No. 4,536,319 to Payne, issued Aug. 20,
1985; all of which are incorporated herein by reference.
The compositions of the present invention can also comprise
mixtures of the above nonionic surfactants.
A thorough discussion of nonionic surfactants for detergent bar and
liquid products is presented by U.S. Pat. No. 5,510,042 to Hartman
et al., and U.S. Pat. No. 4,483,779 to Llenado, et al.,
incorporated herein by reference.
B. Anionic Surfactants
Anionic surfactants include any of the known hydrophobes attached
to a carboxylate, sulfonate, sulfate or phosphate polar,
solubilizing group including salts. Salts may be the sodium,
potassium, ammonium and amine salts of such surfactants. Useful
anionic surfactants can be organic sulfuric reaction products
having in their molecular structure an alkyl group containing from
about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric
acid ester group, or mixtures thereof. (Included in the term
"alkyl" is the alkyl portion of acyl groups.) Examples of this
group of synthetic detersive surfactants which can be used in the
present invention are the alkyl sulfates, especially those obtained
by sulfating the higher alcohols (C.sub.8 -C.sub.18 carbon atoms)
produced from the glycerides of tallow or coconut oil; and alkyl
benzene sulfonates.
Other useful anionic surfactants herein include the esters of
alpha-sulfonated fatty acids preferably containing from about 6 to
20 carbon atoms in the ester group; 2-acyloxyalkane-1-sulfonic
acids preferably containing from about 2 to 9 carbon atoms in the
acyl group and from about 9 to about 23 carbon atoms in the alkane
moiety; alkyl ether sulfates preferably containing from about 10 to
20 carbon atoms in the alkyl group and from about 1 to 30 moles of
ethylene oxide; olefin sulfonates preferably containing from about
12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates
preferably containing from about 1 to 3 carbon atoms in the alkyl
group and from about 8 to 20 carbon atoms in the alkane moiety.
Anionic surfactants based on the higher fatty acids, i.e., "soaps"
are useful anionic surfactants herein. Higher fatty acids
containing from about 8 to about 24 carbon atoms and preferably
from about 10 to about 20 carbon atoms and the coconut and tallow
soaps can also be used herein as corrosion inhibitors.
Preferred water-soluble anionic organic surfactants herein include
linear alkyl benzene sulfonates containing from about 10 to about
18 carbon atoms in the alkyl group; branched alkyl benzene
sulfonates containing from about 10 to about 18 carbon atoms in the
alkyl group; the tallow range alkyl sulfates; the coconut range
alkyl glyceryl sulfonates; alkyl ether (ethoxylated) sulfates
wherein the alkyl moiety contains from about 12 to 18 carbon atoms
and wherein the average degree of ethoxylation varies between 1 and
12, especially 3 to 9; the sulfated condensation products of tallow
alcohol with from about 3 to 12, especially 6 to 9, moles of
ethylene oxide; and olefin sulfonates containing from about 14 to
16 carbon atoms.
Specific preferred anionics for use herein include: the linear
C.sub.10 -C.sub.14 alkyl benzene sulfonates (LAS); the branched
C.sub.10 -C.sub.14 alkyl benzene sulfonates (ABS); the tallow alkyl
sulfates, the coconut alkyl glyceryl ether sulfonates; the sulfated
condensation products of mixed C.sub.10 -C.sub.18 tallow alcohols
with from about 1 to about 14 moles of ethylene oxide; and the
mixtures of higher fatty acids containing from 10 to 18 carbon
atoms.
It is to be recognized that any of the foregoing anionic
surfactants can be used separately herein or as mixtures. Moreover,
commercial grades of the surfactants can contain non-interfering
components which are processing by-products. For example,
commercial alkaryl sulfonates, preferably C.sub.10 -C.sub.14, can
comprise alkyl benzene sulfonates, alkyl toluene sulfonates, alkyl
naphthalene sulfonates and alkyl poly-benzenoid sulfonates. Such
materials and mixtures thereof are fully contemplated for use
herein.
Other examples of the anionic surfactants used herein include fatty
acid soaps, ether carboxylic acids and salts thereof, alkane
sulfonate salts, a-olefin sulfonate salts, sulfonate salts of
higher fatty acid esters, higher alcohol sulfate ester or ether
ester salts, alkyl, preferably higher alcohol phosphate ester and
ether ester salts, and condensates of higher fatty acids and amino
acids.
Fatty acid soaps include those having the formula: R--C(O)OM,
wherein R is C.sub.6 to C.sub.22 alkyl and M is preferably
sodium.
Salts of ether carboxylic acids and salts thereof include those
having the formula: R--(OR.sup.1).sub.n --OCH.sub.2 C(O)OM, wherein
R is C.sub.6 to C.sub.22 alkyl, R.sup.1 is C.sub.2 to C.sub.10,
preferably C.sub.2 alkyl, and M is preferably sodium.
Alkane sulfonate salts and a-olefin sulfonate salts have the
formula: R--SO.sub.3 M, wherein R is C.sub.6 to C.sub.22 alkyl or
a-olefin, respectively, and M is preferably sodium.
Sulfonate salts of higher fatty acid esters include those having
the formula:
wherein R is C.sub.12 to C.sub.22 alkyl, R.sup.1 is C.sub.1 to
C.sub.18 alkyl and M is preferably sodium.
Higher alcohol sulfate ester salts include those having the
formula:
wherein R is C.sub.12 -C.sub.22 alkyl, R.sup.1 is C.sub.1 -C.sub.18
hydroxyalkyl, M is preferably sodium.
Higher alcohol sulfate ether ester salts include those having the
formula:
wherein R is C.sub.12 -C.sub.22 alkyl, R.sup.1 is C.sub.1 -C.sub.18
hydroxyalkyl, M is preferably sodium and x is an integer from 5 to
25.
Higher alcohol phosphate ester and ether ester salts include
compounds of the formulas:
and
wherein R is alkyl or hydroxyalkyl of 12 to 22 carbon atoms,
R.sup.1 is C.sub.2 H.sub.4, n is an integer from 5 to 25, and M is
preferably sodium.
Other anionic surfactants herein are sodium coconut oil fatty acid
monoglyceride sulfonates and sulfates; sodium or potassium salts of
alkyl phenol ethylene oxide ether sulfates containing from about 1
to about 10 units of ethylene oxide per molecule and wherein the
alkyl groups contain from about 8 to about 12 carbon atoms; and
sodium or potassium salts of alkyl ethylene oxide ether sulfates
containing about 1 to about 10 units of ethylene oxide per molecule
and wherein the alkyl group contains from about 10 to about 20
carbon atoms.
C. Cationic Surfactants
Preferred cationic surfactants of the present invention are the
reaction products of higher fatty acids with a polyamine selected
from the group consisting of hydroxyalkylalkylenediamines and
dialkylenetriamines and mixtures thereof.
A preferred component is a nitrogenous compound selected from the
group consisting of:
(i) the reaction product mixtures of higher fatty acids with
hydroxyalkylalkylenediamines in a molecular ratio of about 2:1,
said reaction product containing a composition having a compound of
the formula: ##STR2##
wherein R.sub.1 is an acyclic aliphatic C.sub.15 -C.sub.21
hydrocarbon group and R.sub.2 and R.sub.3 are divalent C.sub.1
-C.sub.3 alkylene groups; commercially available as Mazamide 6 from
PPG;
(ii) the reaction product of higher fatty acids with
dialkylenetriamines in a molecular ratio of about 2:1; said
reaction product containing a composition having a compound of the
formula: ##STR3##
wherein R.sub.1, R.sub.2 and R.sub.3 are as defined above; and
mixtures thereof.
Another preferred component is a cationic nitrogenous salt
containing one long chain acyclic aliphatic C.sub.15 -C.sub.22
hydrocarbon group selected from the group consisting of:
(iii) acyclic quaternary ammonium salts having the formula:
##STR4##
wherein R.sub.4 is an acyclic aliphatic C.sub.15 -C.sub.22
hydrocarbon group, R.sub.5 and R.sub.6 are C.sub.1 -C.sub.4
saturated alkyl or hydroxyalkyl groups, and A [-] is an anion,
especially as described in more detail hereinafter, examples of
these surfactants are sold by Sherex Chemical Company under the
Adgen trademarks;
(iv) substituted imidazolinium salts having the formula:
##STR5##
wherein R.sub.1 is an acyclic aliphatic C.sub.15 -C.sub.21
hydrocarbon group, R.sub.7 is a hydrogen or a C.sub.1 -C.sub.4
saturated alkyl or hydroxyalkyl group, and A [-] is an anion;
(v) substituted imidazolinium salts having the formula:
##STR6##
wherein R.sub.2 is a divalent C.sub.1 -C.sub.3 alkylene group and
R.sub.1, R.sub.5 and A [-] are as defined above; an example of
which is commercially available under the Monaquat ISIES trademark
from Mona Industries, Inc.;
(vi) alkylpyridinium salts having the formula: ##STR7##
wherein R.sub.4 is an acyclic aliphatic C.sub.16 -C.sub.22
hydrocarbon group and A [-] is an anion; and
(vii) alkanamide alkylene pyridinium salts having the formula:
##STR8##
wherein R.sub.1 is an acyclic aliphatic C.sub.15 -C.sub.21
hydrocarbon group, R.sub.2 is a divalent C.sub.1 -C.sub.3 alkylene
group, and A [-] is an ion group; and mixtures thereof.
Another class of preferred cationic nitrogenous salts having two or
more long chain acyclic aliphatic C.sub.15 -C.sub.22 hydrocarbon
groups or one said group and an arylalkyl group are selected from
the group consisting of:
(viii) acyclic quaternary ammonium salts having the formula:
##STR9##
wherein each R.sub.4 is an acyclic aliphatic C.sub.15 -C.sub.22
hydrocarbon group, R.sub.5 is a C.sub.1 -C.sub.4 saturated alkyl or
hydroxyalkyl group, R.sub.8 is selected from the group consisting
of R.sub.4 and R.sub.5 groups, and A [-] is an anion defined as
above; examples of which are commercially available from Sherex
Company under the Adgen trademarks;
(ix) diamido quaternary ammonium salts having the formula:
##STR10##
wherein each R.sub.1 is an acyclic aliphatic C.sub.15 -C.sub.21
hydrocarbon group, R.sub.2 is a divalent alkylene group having 1 to
3 carbon atoms, R.sub.5 and R.sub.9 are C.sub.1 -C.sub.4 saturated
alkyl or hydroxyalkyl groups, and A [-] is an anion; examples of
which are sold by Sherex Chemical Company under the Varisoft
trademark;
(x) diamino alkoxylated quaternary ammonium salts having the
formula: ##STR11##
wherein n is equal to 1 to about 5, and R.sub.1, R.sub.2, R.sub.5
and A [-] are as defined above;
(xi) quaternary ammonium compounds having the formula:
##STR12##
wherein each R.sub.4 is an acyclic aliphatic C.sub.15 -C.sub.22
hydrocarbon group, each R.sub.5 is a C.sub.1 -C.sub.4 saturated
alkyl or hydroxyalkyl group, and A [-] is an anion; examples of
such surfactants are available from Onyx Chemical Company under the
Ammonyx.RTM. 490 trademark;
(xiii) substituted imidazolinium salts having the formula:
##STR13##
wherein each R.sub.1 is an acyclic aliphatic C.sub.15 -C.sub.21
hydrocarbon group, R.sub.2 is a divalent alkylene group having 1 to
3 carbon atoms, and R.sub.5 and A [-] are as defined above;
examples are commercially available from Sherex Chemical Company
under the Varisoft 475 and Varisoft 445 trademarks; and
(vi) substituted imidazolinium salts having the formula:
##STR14##
wherein R.sub.1, R.sub.2 and A - are as defined above; and mixtures
thereof.
The more preferred cationic conventional surfactant is selected
from the group consisting of an alkyltrimethylammonium salt, a
dialkyldimethylammonium salt, an alkyldimethylbenzylammonium salt,
an alkylpyridinium salt, an alkylisoquinolinium salt, benzethonium
chloride, and an acylamino acid cationic surfactant.
Anion A
In the cationic nitrogenous salts herein, the anion A [-] provides
electrical neutrality. Most often, the anion used to provide
electrical neutrality in these salts is a halide, such as chloride,
bromide, or iodide. However, other anions can be used, such as
methylsulfate, ethylsulfate, acetate, formate, sulfate, carbonate,
and the like. Chloride and methylsulfate are preferred herein as
anion A.
Cationic surfactants are commonly employed as fabric softeners in
compositions added during the rinse cycle of clothes washing. Many
different types of fabric conditioning agents have been used in
rinse cycle added fabric conditioning compositions as disclosed by
U.S. Pat. No. 5,236,615, Trinh et al. and U.S. Pat. No. 5,405,542,
Trinh et al., both patents herein incorporated by reference in
their entirety. The most favored type of agent has been the
quaternary ammonium compounds. Many such quaternary ammonium
compounds are disclosed for example, by U.S. Pat. No. 5,510,042,
Hartman et al. incorporated herein by reference in its entirety.
These compounds may take the form of noncyclic quaternary ammonium
salts having preferably two long chain alkyl groups attached to the
nitrogen atoms. Additionally, imidazolinium salts have been used by
themselves or in combination with other agents in the treatment of
fabrics as disclosed by U.S. Pat. No. 4,127,489, Pracht, et al.,
incorporated herein by reference in its entirety. U.S. Pat. No.
2,874,074, Johnson discloses using imidazolinium salts to condition
fabrics; and U.S. Pat. No. 3,681,241, Rudy, and U.S. Pat. No.
3,033,704, Sherrill et al. disclose fabric conditioning
compositions containing mixtures of imidazolinium salts and other
fabric conditioning agents. These patents are incorporated herein
by reference in their entirety.
D. Amphoteric Surfactants
Amphoteric surfactants have a positive or negative charge or both
on the hydrophilic part of the molecule in acidic or alkaline
media.
Examples of the amphoteric surfactants which can be used herein
include amino acid, betaine, sultaine, phosphobetaines,
imidazolinium derivatives, soybean phospholipids, and yolk
lecithin. Examples of suitable amphoteric surfactants include the
alkali metal, alkaline earth metal, ammonium or substituted
ammonium salts of alkyl amphocarboxy glycinates and alkyl
amphocarboxypropionates, alkyl amphodipropionates, alkyl
amphodiacetates, alkyl amphoglycinates and alkyl amphopropionates
wherein alkyl represents an alkyl group having 6 to 20 carbon
atoms. Other suitable amphoteric surfactants include
alkyliminopropionates, alkyl iminodipropionates and alkyl
amphopropylsulfonates having between 12 and 18 carbon atoms,
alkylbetaines and amidopropylbetaines and alkylsultaines and
alkylamidopropylhydroxy sultaines wherein alkyl represents an alkyl
group having 6 to 20 carbon atoms are especially preferred.
Particularly useful amphoteric surfactants include both mono and
dicarboxylates such as those of the formulae: ##STR15##
wherein R is an alkyl group of 6-20 carbon atoms, x is 1 or 2 and M
is hydrogen or sodium. Mixtures of the above structures are
particularly preferred.
Other formulae for the above amphoteric surfactants include the
following: ##STR16## ##STR17## ##STR18## ##STR19##
where R is an alkyl group of 6-20 carbon atoms.
Of the above amphoteric surfactants, particularly preferred are the
alkali salts of alkyl amphocarboxyglycinates and alkyl
amphocarboxypropionates, alkyl amphodipropionates, alkyl
amphodiacetates, alkyl amphoglycinates, alkyl amphopropyl
sulfonates and alkyl amphopropionates wherein alkyl represents an
alkyl group having 6 to 20 carbon atoms. Even more preferred are
compounds wherein the alkyl group is derived from coconut oil or is
a lauryl group, for example, cocoamphodipropionate. Such
cocoamphodipropionate surfactants are commercially sold under the
trademarks Miranol C2M-SF CONC. and Miranol FBS by Rhodia Inc.
Other commercially useful amphoteric surfactants are available from
Rhodia Inc. and include:
cocoamphoacetate (sold under the trademarks MIRANOL CM CONC. and
MIRAPON FA), cocoamphopropionate (sold under the trademarks MIRANOL
CM- SF CONC. and MIRAPON FAS), cocoamphodiacetate (sold under the
trademarks MIRANOL C2M CONC. and MIRAPON FB), lauroamphoacetate
(sold under the trademarks MIRANOL HM CONC. and MIRAPON LA),
lauroamphodiacetate (sold under the trademarks MIRANOL H2M CONC.
and MIRAPON LB), lauroamphodipropionate (sold under the trademarks
MIRANOL H2M SF CONC. AND MIRAPON LBS), lauroamphodiacetate (sold
under the trademark MIRANOL BM obtained from a mixture CONC.), and
of lauric and myristic acids cocoamphopropyl (sold under the
trademark MIRANOL CS sulfonate CONC.)
Somewhat less preferred are:
caproamphodiacetate (sold under the trademark MIRANOL S2M CONC.),
caproamphoacetate (sold under the trademark MIRANOL SM CONC.),
caproamphodipropionate (sold under the trademark MIRANOL S2M- SF
CONC.), and stearoamphoacetate (sold under the trademark MIRANOL
DM).
II. Gemini Surfactants
Gemini surfactants form a special class of surfactant. These
surfactants have the general formula:
and get their name because they comprise two surfactant moieties
(A,A.sup.1) joined by a spacer (G), wherein each surfactant moiety
(A,A,.sup.1) has a hydrophilic group and a hydrophobic group.
Generally, the two surfactant moieties (A,A.sup.1) are twins, but
they can be different.
The gemini surfactants are advantageous because they have low
critical micelle concentrations (cmc) and, thus, lower the cmc of
solutions containing both a gemini surfactant and a conventional
surfactant. Lower cmc causes better solubilization and increased
detergency at lower surfactant use levels and unexpectedly enhances
the deposition of the soil release polymers as claimed by this
invention with demonstrated results to follow herein. Soil removal
agents adhere to the fabric being laundered, much better than when
mixed with only non-gemini, conventional surfactants.
Also, the gemini surfactants result in a low pC.sub.20 value and
low Krafft points. The pC.sub.20 value is a measure of the
surfactant concentration in the solution phase that will reduce the
surface tension of the solvent by 20 dynes/cm. It is a measure of
the tendency of the surfactant to adsorb at the surface of the
solution. The Krafft point is the temperature at which the
surfactant's solubility equals the cmc. Low Krafft points imply
better solubility in water, and lead to greater latitude in making
formulations.
Unexpectedly, the mixture of gemini surfactant with the above
mentioned conventional surfactant, and the above-mentioned
polymeric soil release agent, dramatically enhances the deposition
of the soil release agent. The aforementioned mixture is far more
effective than conventional surfactant and soil release agent
formulations without the gemini surfactants.
A number of the gemini surfactants are reported in the literature,
see for example, Okahara et al., J. Japan Oil Chem. Soc. 746
(Yukagaku) (1989); Zhu et al., 67 JAOCS 7,459 (July 1990); Zhu et
al., 68 JAOCS 7,539 (1991); Menger et al., J. Am. Chemical Soc.
113, 1451 (1991); Masuyama et al., 41 J. Japan Chem. Soc. 4,301
(1992); Zhu et al., 69 JAOCS 1,30 (January 1992); Zhu et al., 69
JAOCS 7,626 July 1992); Menger et al., 115 J. Am. Chem. Soc. 2,
10083 (1993); Rosen, Chemtech 30 (March 1993); and Gao et al., 71
JAOCS 7,771 (July 1994), all of this literature incorporated herein
by reference.
A number of gemini surfactants have also been disclosed in the
patent literature including U.S. Pat. No. 5,160,450 to Okahara et
al., U.S. Pat. No. 3,244,724 to Guttman, U.S. Pat. Nos. 2,524,218
and 2,530,147 to Bersworth (three hydrophilic heads) and U.S. Pat.
No. 2,374,354 to Kaplan.
The present invention then, is comprised of the discovery of novel
cationic surfactants comprised of multiple hydrophilic/hydrophobic
chains and their use along with other known cationic and amphoteric
gemini surfactants in combination with a second conventional
surfactant and a polymeric soil release agent so as to provide
enhanced cleaning and soil release properties in laundry detergents
and the like.
The novel cationic surfactants useful in the practice of the
present invention are composed of trimeric and tetrameric
hydrophilic/hydrophobic chains or tails as represented by the
structures below: ##STR20##
wherein R is a C.sub.5 -C.sub.22 alkyl, aryl, alkylaryl and the
perfluorinated- and hydroxy-substituted derivatives thereof;
R.sub.1 is a C.sub.1 -C.sub.4 alkyl and R.sub.2 is a C.sub.2
-C.sub.12 alkylene, arylene or alkylarylene and Y independently
represents an anion such as Br.sup.-, Cl.sup.-, methosulfate,
alkosulfate and the like.
Specific trimeric and tetrameric cationic gemini surfactants of the
present invention may be represented as follows: ##STR21##
wherein R has been hereinbefore defined. Preferred compounds
comprise methylalkyl-bis(3-(dimethyl-alkylammonio)propyl) ammonium
tribromide. ##STR22##
wherein R has been hereinbefore defined. Preferred compounds
comprise methylalkyl-bis(6-(dimethyl-alkylammonio)hexyl) ammonium
tribromide. ##STR23##
wherein R has been hereinbefore defined. Preferred compounds
comprise
methyldodecyl-bis(3-(dimethyldodecylammonio)propyl]ammonium
tribromide and
methyldodecyl-bis[6-(dimethyldodecylammonio)hexyl]ammonium
tribromide.
The trimer and tetramer gemini species can be prepared as follows:
##STR24##
A second trimeric cationic structure can be prepared as follows:
##STR25##
The tetrameric cationic gemini surfactant is prepared by the same
pathways utilizing H.sub.2 N--(CH.sub.2).sub.3
--NH--(CH.sub.2).sub.6 --NH--(CH.sub.2).sub.6 --NH.sub.2 as the
starting material. Similar pathways are disclosed in two articles
by Zana et al., Langmuir 7 1072-1075 (1991) and Langmuir 10
1448-1457 (1995) which are hereby incorporated by reference.
These new tetrameric cationic surfactants can be used together with
the conventional linear surfactant as discussed, supra, in
combination with the polymeric soil release agent to surprisingly
and unexpectedly provide enhanced and superior cleaning and soil
release properties in laundry detergents and other like
compositions. Other known cationic gemini surfactants can be used
in place of the novel trimer and tetranier species if desired.
Generically, these gemini surfactants can be represented by the
structure: ##STR26##
wherein R is a C.sub.5 -C.sub.22 alkyl, aryl, alkylaryl and the
perfluorinated- and hydroxy-substituted derivatives thereof and
carboxyalkyl; R.sub.1 is a C.sub.1 -C.sub.4 alkyl; X independently
represents --O--; --S--; (--CH.sub.2 --).sub.n ; or ##STR27##
wherein n is a number of from about 1-25; m is a number of from
about 1-4 and p is a number of from about 1 to 50 and Y is a
halogen, CH.sub.3 SO.sub.4.sup.- and CH.sub.2 CH.sub.2
SO.sub.4.sup.-.
More specifically, the cationic gemini surfactants useful in the
compositions of the present invention include compounds with the
structures: ##STR28##
wherein R, R.sub.1, p and Y have been hereinbefore defined.
##STR29##
wherein R, R.sub.1 and Y have been hereinbefore defined.
##STR30##
wherein R, R.sub.1 and Y have been hereinbefore defined.
##STR31##
wherein R, R.sub.1 and Y have been hereinbefore defined.
##STR32##
wherein R, R.sub.1 and Y have been hereinbefore defined.
##STR33##
wherein R, R.sub.1 and Y have been hereinbefore defined.
Another group of cationic gemini surfactants useful in the
detergent compositions of the present invention include quaternary
cationic surfactants having two imidazoline groups that are
connected by an alkylene bridge. These surfactants may be
structurally represented as follows: ##STR34##
wherein R.sub.1 independently represents alkyl, hydroxy-substituted
or perfluorinated alkyl of from about 5 to about 22 carbon atoms;
R.sub.2 represents alkylene and the hydroxy-substituted derivatives
thereof, alkylaryl of 1 to about 10 carbon atoms and the
hydroxy-substituted derivatives thereof or R.sub.3 --D--R.sub.3
wherein R.sub.3 independently represents alkylene of from 1 to
about 6 carbon atoms and the hydroxy-substituted derivatives
thereof as well as aryl, and D represents --O--, --S--, --SO.sub.2
--, a polyether group [--O(R.sub.4).sub.x --] or aryl wherein
R.sub.4 independently represents about C.sub.2 to about C.sub.4
alkyl with x being a number from 1 to 20 and X independently
represents an alkyl of 1 to 10 carbon atoms and the
hydroxy-substituted derivatives thereof and alkylaryl; and Y
independently represents an anion.
These surfactants and the process for their preparation are more
specifically described in U.S. Pat. No. 5,643,498 to Li et al.
which is hereby incorporated by reference.
Some of the compounds such as those described above are set forth
more fully in U.S. Pat. No. 5,534,197 to Schiebel et al. which
description is incorporated herein by reference.
A second group of gemini surfactants that are amphoteric in nature
also exhibit surprising and unexpectedly good soil release
properties when used with the aforementioned polymers. These
surfactants may be structurally represented as follows:
##STR35##
wherein R is a C.sub.6 to C.sub.18 alkyl, aryl and the
hydroxy-substituted derivatives thereof, preferably derived from
coconut fatty acid, (--CH.sub.3 (CH.sub.2).sub.n COOH wherein n is
a number of from 6 to 18), stearyl (CH.sub.3 (CH.sub.2).sub.16
COOH) or palmityl (CH.sub.3 (CH.sub.2).sub.14 COOH). More
preferably, the compounds are selected from the group consisting of
N'N'bis(2-lauramidoethyl)ethylenediamine diamine;
-N'N'di(acetate)-N'N'bis(2-
lauramidoethyl)ethylenediamine-N'N'di(propionate);
N'N'bis(2-lauramidoethylethylenediamine-N'N'-di(-2-hydroxy-propyl
sulfonate).
With respect to the compounds useful in the present invention, many
of the moieties can be derived from natural sources which will
generally contain mixtures of different saturated and unsaturated
carbon chain lengths. The natural sources can be illustrated by
coconut oil or similar natural oil sources such as palm kernel oil,
palm oil, soy oil, rapeseed oil, castor oil or animal fat sources
such as herring oil and beef tallow. Generally, the fatty acids
from natural sources in the form of the fatty acid or the
triglyceride oil can be a mixture of alkyl radicals containing from
about 5 to about 22 carbon atoms. Illustrative of the natural fatty
acids are caprylic (C.sub.8), capric (C.sub.10), lauric (C.sub.12),
myristic (C.sub.14), palmitic (C.sub.16), stearic (C.sub.18), oleic
(C.sub.18, mono-unsaturated), linoleic (C.sub.18, di-unsaturated),
linolenic (C.sub.18, tri-unsaturated), ricinoleic (C.sub.18,
mono-unsaturated) arachidic (C.sub.20), gadolic (C.sub.20,
mono-unsaturated), behenic (C.sub.22) and erucic (C.sub.22). These
fatty acids can be used per se, as concentrated cuts or as
fractionations of natural source acids. The fatty acids with even
numbered carbon chain lengths are given as illustrative though the
odd numbered fatty acids can also be used. In addition, single
carboxylic acids,e.g., lauric acid, or other cuts, as suited for
the particular application, may be used.
Where desired, the cationic gemini surfactants used in the present
invention can be oxyalkylated by reacting the product with an
alkylene oxide according to known methods, preferably in the
presence of an alkaline catalyst. The free hydroxyl groups of the
alkoxylated derivative can then be sulfated, phosphated or acylated
using normal methods such as sulfation with sulfamic acid or sulfur
trioxide-pyridine complex, or acylation with an acylating agent
such as a carboxylic acid, ester, and the naturally occurring
triglyceride esters thereof.
For alkylation conditions and commonly used alkylating agents, see
Amphoteric Surfactants Vol. 12, Ed. B. R. Bluestein and C. L.
Hilton, Surfactant Science Series 1982, pg. 17 and references cited
therein, the disclosures of which are incorporated herein by
reference.
For sulfation and phosphation, see Surfactant Science Series, Vol.
7, Part 1, S. Shore & D. Berger, page 135, the disclosure of
which is incorporated herein by reference. For phosphating review,
see Surfactant Science Series, Vol. 7, Part II, E. Jungermann &
H. Silbertman, page 495, the disclosure of which is incorporated
herein by reference.
The surfactant compositions of the invention are extremely
effective in aqueous solution at low concentrations as defined
herein. The surfactants of the invention can be used in any amount
needed for a particular application which can be easily determined
by a skilled artisan without undue experimentation.
III. Polymeric Soil Release Agents
Soil release agents, usually polymers, are especially desirable
additives for releasing hydrophobic stains from textile fibers
especially synthetics and also are used as effective particle
suspending agents for liquid detergent, and fabric softener
systems. Suitable soil release agents are disclosed in U.S. Pat.
Nos.: 4,956,477; 4,702,857; 4,713,194; and 4,711,730 all to
Gosselink et al.; U.S. Pat. No. 4,877,896 to Maldonado, et al.;
U.S. Pat. No. 4,873,003 to O'Lenick et al.; U.S. Pat. No. 4,999,128
to Sonenstein; U.S. Pat. No. 4,749,596 to Evans, and U.S. Pat. No.
5,236,615 to Trinh et al., said patents being incorporated herein
by reference. Typical soil release agents include nonionic or
anionic polymers, or mixtures thereof.
Especially effective polymeric soil release agents are the block
copolymers of polyalkylene terephthalate and polyoxyethylene
terephthalate, and block copolymers of polyalkylene terephthalate
and polyethylene glycol. The polyalkylene terephthalate blocks
preferably comprise ethylene and/or propylene alkylene groups. Many
of such soil release polymers are nonionic. More specifically,
these polymers are comprised of repeating units of ethylene and/or
propylene terephthalate and polyethylene oxide terephthalate,
preferably at a molar ratio of ethylene terephthalate units to
polyethylene oxide terephthalate units of from about 25:75 to about
35:65, said polyethylene oxide terephthalate containing
polyethylene oxide blocks having molecular weights of from about
300 to about 2000. The molecular weight of these polymeric soil
release agents is in the range of from about 4,000 to about 55,000.
Other useful soil release polymers include, but are not limited to,
sulfonated polyethylene terephthalate, polyester urethane, and
acetic acid ethenyl esters; the polyethylene
terephthalate/polyoxyethylene terephthalate (PET--POET) polymer
being most preferable. Typically, molecular weight ranges of these
polymers are from 500 to 120,000, preferably, 2000 to 35,000, and
most preferably 2000 to 25,000.
U.S. Pat. No. 4,976,879 to Maldonado et al. discloses specific
preferred soil release agents which can also provide improved
antistatic benefits; said patent being incorporated herein by
reference.
Another preferred polymeric soil release agent is a crystallizable
polyester with repeat units of ethylene terephthalate containing
from about 10% to about 15% by weight of ethylene terephthalate
units together with from about 10% to about 50% by weight of
polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of average molecular weight of from about 300 to about
6,000, and the molar ratio of ethylene terephthalate units to
polyoxyethylene terephthalate units in the crystallizable polymeric
compound is between 2:1 and 6:1. Examples of this polymer include
the commercially available materials Zelcon 4780 (from DuPont) and
Milease T (from ICI).
A more complete disclosure of these highly preferred soil release
agents is contained in European Patent Application 185,427,
Gosselink, published Jun. 25, 1986, incorporated herein by
reference.
A preferred nonionic soil release polymer has the following average
structure: ##STR36##
Such soil release polymers are described in U.S. Pat. No.
4,849,257, Borcher, et al., this patent being incorporated herein
by reference.
Another preferred nonionic soil release polymer has the following
average structure: ##STR37##
wherein n is preferably between about 50 to about 150.
Another preferred nonionic soil release polymer is described in now
abandoned U.S. patent application Ser. No. 07/676,682, filed Mar.
28, 1991, by Pan, et al., for Nonionic Soil Release Agents.
The most preferred nonionic soil release agents are the REPEL-O-TEX
line of soil release agents sold by Rhone-Poulenc Inc., Cranbury,
N.J. These products include REPEL-O-TEX SRP3, REPEL-O-TEX SRP4,
REPEL-O-TEX QCJ product and REPEL-O-TEX QCX products. VELVETOL 251C
is a 100% active hydrophilic polyester from which REPEL-O-TEX SRP3,
SRP4, AND QCJ are manufactured at different polymer concentrations.
The polymers have a molecular weight of from about 3,000 to about
10,000. REPEL-O-TEX QCJ product is a 15 weight percent active
dispersion of the above mentioned polymer for liquid laundry
detergents, whereas SRP3 and SRP4 are diluted with sodium sulfate
for powder detergent applications. The polymers of the REPEL-O-TEX
products are nonionic polyester-polyether (PET--POET)
transesterification co-polymers. The REPEL-O-TEX QCX is a higher
molecular weight hydrophilic polyester polymer with a molecular
weight range of from about 10,000 to about 35,000.
Suitable anionic polymeric or oligomeric soil release agents are
disclosed in U.S. Pat. No. 4,018,569 to Trinh, and U.S. Pat. No.
4,787,989 to Fanelli, et al. Other suitable polymers are disclosed
in U.S. Pat. No. 4,808,086 to Evans et al.; all of these patents
being incorporated herein by reference.
Cationic polymeric soil release agents are also useful in the
present invention. Suitable cationic soil release polymers are
described in U.S. Pat. No. 4,956,447 to Gosselink, et al. and U.S.
Pat. No. 4,873,003 to O'Lenick, et al.; and U.S. Pat. No. 5,405,542
to Trinh et al. These patents are also incorporated by
reference.
IV. Auxiliary Detergent Ingredients
A. Detergency Builders
Compositions of the present invention may include detergency
builders selected from any of the conventional inorganic and
organic water-soluble builder salts, including neutral or alkaline
salts, as well as various water-insoluble and so-called "seeded"
builders.
Builders are preferably selected from the various water-soluble,
alkali metal, ammonium or substituted ammonium phosphates,
polyphosphates, phosphonates, polyphosphonates, carbonates,
silicates, borates, polyhydroxysulfonates, polyacetates,
carboxylates, and polycarboxylates. Most preferred are the alkali
metal, especially sodium, salts of the above.
Specific examples of inorganic phosphate builders are sodium and
potassium tripolyphosphate, pyrophosphate, polymeric metaphate
having a degree of polymerization of from about 6 to 21, and
orthophosphate. Examples of polyphosphonate builders are the sodium
and potassium salts of ethylene-1, 1-diphosphonic acid, the sodium
and potassium salts of ethane 1-hydroxy-1,1-diphosphonic
-diphosphonic acid and the sodium and potassium salts of ethane,
1,1,2-triphosphonic acid.
Examples of nonphosphorus, inorganic builders are sodium and
potassium carbonate, bicarbonate, sesquicarbonate, tetraborate
decahydrate, and silicate having a molar ratio of SIO.sub.2 to
alkali metal oxide of from about 0.5 to about 4.0, preferably from
about 1.0 to about 2.4.
Water-soluble, nonphosphorus organic builders useful herein include
the various alkali metal, ammonium and substituted ammonium
polyacetates, carboxylates, polycarboxylates and
polyhydroxysulfonates. Examples of polyacetate and polycarboxylate
builders are the sodium, potassium, lithium, ammonium and
substituted ammonium salts of ethylenediamine tetraacetic acid,
nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids, and citric acid.
Highly preferred polycarboxylate builders herein are set forth in
U.S. Pat. No. 3,308,067 to Diehl, issued Mar. 7, 1967 which is
incorporated herein by reference. Such materials include the
water-soluble salts of homo- and copolymers of aliphatic carboxylic
acids such as maleic acid, itaconic acid, mesaconic acid, fumaric
acid, aconitic acid, citraconic acid and methylenemalonic acid.
Other builders include the carboxylated carbohydrates of U.S. Pat.
No. 3,723,322 to Diehl that is incorporated herein by
reference.
Other useful builders herein are sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate,
cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate
phloroglucinol trisulfonate, water-soluble polyacrylates (having
molecular weights of from about 2,000 to about 200,000 for
example), and the copolymers of maleic anhydride with vinyl methyl
ether or ethylene.
Other suitable polycarboxylates for use herein are the polyacetal
carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13,
1979 and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 both to
Crutchfield et al., which are incorporated herein by reference.
"Insoluble" builders include both seeded builders such as 3:1
weight mixtures of sodium carbonate and calcium carbonate; and
2.7:1 weight mixtures of sodium sesquicarbonate and calcium
carbonate. Amphorus and crystalline alumino silicates such as
hydrated sodium Zeolite A are commonly used in laundry detergent
applications. They have a particle size diameter of 0.1 micron to
about 10 microns depending on water content of these molecules.
These are referred to as ion exchange materials. Crystalline
alumino silicates are characterized by their calcium ion exchange
capacity. Amphorus alumino silicates are usually characterized by
their magnesium exchange capacity. They can be naturally occurring
or synthetically derived.
A detailed listing of suitable detergency builders can be found in
U.S. Pat. No. 3,936,537, supra, incorporated herein by
reference.
B. Miscellaneous Detergent Ingredients
Detergent composition components may also include hydrotropes,
enzymes (e.g., proteases, amylases and cellulases), enzyme
stabilizing agents, pH adjusting agents (monoethanolamine, sodium
carbonate, etc.) halogen bleaches (e.g., sodium and potassium
dichloroisocyanurates), peroxyacid bleaches (e.g.,
diperoxydodecane-1,12-dioic acid), inorganic percompound bleaches
(e.g., sodium perborate), antioxidants as optional stabilizers,
reductive agents, activators for percompound bleaches (e.g.,
tetraacetylethylenediamine and sodium nonanoyloxybenzene
sulfonate), soil suspending agents (e.g., sodium carboxymethyl
cellulose), soil anti-redisposition agents, corrosion inhibitors,
perfumes and dyes, buffers, whitening agents, solvents (e.g.,
glycols and aliphatic alcohols) and optical brighteners. Any of
other commonly used auxiliary additives such as inorganic salts and
common salt, humectants, solubilizing agents, UV absorbers,
softeners, chelating agents, static control agents and viscosity
modifiers may be added to the detergent compositions of the
invention.
For bar compositions, processing aids are optionally used such as
salts and/or low molecular weight alcohols such as monodihydric,
dihydric (glycol, etc.), trihydric (glycerol, etc.), and polyhydric
(polyols) alcohols. Bar compositions may also include insoluble
particulate material components, referred to as "fillers" such as
calcium carbonate, silica and the like.
V. Composition Concentrations
The total weight percentages of the conventional surfactants of the
present invention, all weight percentages being based on the total
active weight of the compositions of this invention consisting of
conventional surfactant(s), gemini surfactant(s), soil release
agent(s), and (optionally) detergency builder(s) are about 10 to
about 99.9 weight percent, preferably about 15-75 weight
percent.
The gemini surfactants are suitably present at a level of about
0.005 to about 50, preferably from about 0.02-15.0, active weight
percent of the composition.
The polymeric soil release agents, are suitably employed at a level
of from about 0.05 to about 40, preferably from about 0.2-15 active
weight percent.
The optional detergency builders are suitably present at a level of
from about 0 to about 70 weight percent, preferably from about 5 to
about 50 weight percent.
VI. Detergent and/or Fabric Softener Compositions
In the preparation of detergent and/or fabric softening
compositions, other optional ingredients such as bleaches, enzymes,
antioxidants, reductive agents, perfumes, fabric brighteners and
the like may be included in amounts each of from about 0 to about 5
weight percent based on the active weight of the composition.
Specific to fabric softener compositions, they generally comprise
from about 10 to 80 active weight percent cationic conventional
surfactant; about 0.005 to about 20, preferably 0.02-10 active
weight percent gemini surfactant. The gemini surfactant may be
cationic, nonionic, amphoteric or mixtures thereof. They also
contain about 0.1 to about 5, preferably about 0.2-3.0, most
preferably about 0.2 to about 1.5 weight percent of polymeric soil
release agent. Gemini/polymer synergy enhances soil release and
general detergency boosting benefits, and improves
suspending/stabilizing properties of the polymeric suspending
agents.
Other optional ingredients for liquid detergents include liquid
carriers and adjuvants as disclosed by U.S. Pat. No. 5,402,542 to
Trinh et al. which is incorporated herein by reference in its
entirety.
The liquid carrier is preferably selected from the group consisting
of water and mixtures of the water and short chain C.sub.1 -C.sub.4
monohydric alcohols. The water used can be distilled, deionized, or
tap water. Mixtures of water and up to about 15% of a short chain
alcohol such as ethanol, propanol, isopropanol or butanol, and
mixtures thereof, are useful as the carrier liquid.
Adjuvants can be added to the softener compositions for their known
purposes. Such adjuvants include, but are not limited to, clays,
viscosity control agents, perfumes, emulsifiers, preservatives,
anti-foaming agents, antioxidants, bactericides, fingicides,
brighteners, opacifiers, freeze-thaw control agents, shrinkage
control agents, and agents to provide ease of ironing. These
adjuvants, if used, are added at their usual levels, generally each
of up to about 5% by active weight of the composition.
The fabric softener compositions can be prepared by conventional
methods such as those disclosed in U.S. Pat. No. 5,405,542 to Trinh
et al.
The present invention is further illustrated by the following
non-limiting examples.
EXAMPLES
To explore the benefits of employing the cationic gemini
surfactants together with conventional surfactants and soil release
polymers, the following examples were run. Tables in the present
specification list the resulting data. In the examples, the
TERG-O-TOMETER, which is a laboratory scale apparatus designed to
simulate the washing process under controlled conditions, was used
to evaluate soil release performance. It is manufactured by United
Testing Company of Hoboken, N.J.
The soil release test procedure of these examples involved a
prewash cycle (cloths repeatedly being washed before staining).
Clean fabrics, two DACRON single knit (DSK), two DACRON double knit
(DDK) and two DACRON/cotton blend (D65/C35) from Scientific
Services, or two pieces of cotton fabric, were prewashed for 12
minutes at 120.degree. F., with 150 ppm (2/1 Ca++/Mg++) water
hardness and cold water rinse.
After drying for 45 minutes on a "high" dryer setting, swatches
were stained with three drops of dirty motor oil. Swatches were
allowed to wick overnight. The stained swatches were washed once
under the same prewash conditions. The same formulas used in the
prewash were used in the final wash.
Evaluation was performed by making the following measurements:
Rd.sub.1 =Average reflectance of prewashed fabric
Rd.sub.2 =Average reflectance of wicked cloth
Rd.sub.3 =Average reflectance of cleaned cloth
Then % soil removed scores listed on the Tables for the examples
was calculated as follows:
It is noted that in all the examples, all like ingredient
abbreviations or designations indicate like ingredients.
Examples 1-3 and Comparative Examples 1-3
Compositions of the present invention were tested for effectiveness
by measuring reflectance. A higher reflectance number means a
cleaner fabric. According to the above test procedure, samples of
the fabric were each washed five (5) times at 120.degree. F. for 12
minutes. Detergent concentration was used at 1 gm. per liter which
is usually the recommended commercial use level. Dirty motor oil
was then added to the fabric and the fabric was allowed to wick
overnight. Afterwards, the oily fabric was washed once in a washing
solution having the same composition used previously (in the
prewash) and the fabric's reflectance was measured using
Spectrogard equipment, common in the industry and available from
BYK-Gardner.
In these Examples 1-3 and Comparative Examples 1-3, the base
detergent is an anionic detergent having an all anionic surfactant
package except for Neodol 25-9 (1.3%). The composition is listed in
TABLE A. These examples and comparative examples all employ 1
active weight percent REPEL-O-TEX SRP3 polymeric soil release
polymer. This SRP is composed of 50% VELVETOL 251C (polymer having
a molecular weight range of 3,000-10,000) and 50% sodium
sulfate.
TABLE A Ingredients of Anionic Detergent Base A Weight % LAS.sup.1
6.0% PS-603.sup.2 6.6 NEODOL 25-9.sup.3 1.3 Na-Sulfate.sup.4 8.3
LSB.sup.5 8.1 Na-Carbonate.sup.9 30.0 Silicate.sup.7 1.2
Zeolite.sup.8 29.3 Perborate.sup.9 0.6 Water.sup.10 2.3
Additives.sup.11 QS Notes: .sup.1 Linear alkyl benzene sulfonate
.sup.2 Linear ether sulfate-12-15 C's chain, 3EO .sup.3 Linear
alcohol ethoxylate, 12-15 C's .sup.4 Sodium sulfate .sup.5 Sodium
lauryl sulfate .sup.6 Sodium carbonate .sup.7 Sodium silicate
.sup.8 Builder Zeolite A .sup.9 Bleach .sup.10 Deionized .sup.11
Additives
The amount of the gemini surfactant is listed as active weight
percent employed. The soil release polymer, gemini surfactants,
etc., were formulated as detergent compositions with Base A above.
In the following tables, SRP is the abbreviation for soil release
polymer, DK means double knit, SK means single knit and cotton/poly
refers to cotton/polyester fabrics. The numbers given for the
respective detergent formulations and clothing material represent
the percentages of soil removed from the clothing. The higher the
number, the greater the degree of soil removed from the fabric
indicating the greater amount of soil release polymer deposited
thereon. The washing conditions at which the formulations were
tested are also given. Pre-wash refers to washing the fabric before
staining so that the copolymer is deposited on the fabric.
5.times., 8.times. etc., means the number of times the fabric was
pre-washed.
Example 1
Soil Removal: Detergent Base A+SRP3 w/quaternary Cationic
Geminis
Washing Conditions:
150 ppm Water
Temp 100.degree. F.
% based on active
TABLE 1 5x Pre-Wash Dacron/ Dacron/ Cotton/ Sample DK SK Poly Base
A + 1.0% SRP3 + 1.5% ethylene bis- -2 82 37.5 (methyl
laurimidazoline)dimethosulfate Base A + 1.0% SRP3 + 1.5%
conventional 2.1 7 2 non-gemini amphoteric surfactant Base A + SRP3
2.0 8.0 9.0
Example 2
Soil Removal: Gemini Surfactants (Linear Alcohol Ethoxylates)
w/SRP3 in Detergent Base A (15%)
Washing Conditions:
150 ppm Water
Temp 120.degree. F.
% based on active
TABLE 2 5x Pre-Wash Dacron/ Dacron/ Cotton/ Sample DK SK Poly 1%
SRP3 + 1% Methyldodecyl-bis[3- 39.5 81 50
(dimethyldodecylammonio)propyl]- ammonium tribromide Base A + SRP3
2.0 8.0 9.0
Example 3
Soil Removal: Linear Alcohol Ethoxylates and Trimeric Gemini
Surfactants @ Lower Temp. (100.degree. F.) in Detergent Base A
Washing Conditions:
150 ppm Water
Temp 100.degree. F.
% based on active
TABLE 3 8x Pre-Wash Dacron/ Dacron/ Cotton/ Sample DK SK Poly 1%
SRP3 + 1% Hexanediyl-1,6- 39.5 91.5 48 bis(dodecyldimethylammonium
bromide) Base A + SRP3 2.0 8.0 9.0
Examples 1-3 are summarized as Table 1 and the respective soil
release polymer and gemini surfactants were formulated with the
other ingredients as set forth above. The numbers given are the
percentages of the soil removed from the various articles of
clothing. The washing conditions for each example are given.
As can be seen from the high levels of soil release that were
achieved, the combination of the gemini surfactants or the multiple
hydrophilic/hydrophobic chain surfactants with the soil release
polymer and conventional surfactant provides superior soil release
properties that surprisingly and unexpectedly enhances the cleaning
efficacy of these compositions at different washing conditions when
compared to the known laundry detergents of the prior art. In other
words, the data clearly shows that the addition of the cationic or
amphoteric gemini surfactant as well as the multiple
hydrophilic/hydrophobic chain surfactants dramatically increase the
deposition and effectiveness of the soil release polymer on the
fabric and hence results in cleaner clothes.
Although the subject matter has been described with respect to the
preferred embodiments, it will be readily apparent to those having
ordinary skill in the art to which the invention pertains that
changes and modifications may be made thereto without departing
from the spirit or scope of the present invention as defined by the
following claims.
* * * * *